Process of extracting glycerin from vinasses.



I, necessary to cool the amyl solution in. order 00' glycerin.

UNITED STATES Parana? OFFICE.

GASTON PHILIYIPE GUIGNARD, OF' MELUN, AND HENRI LOUIS .A'DOLPHE MAME WATBIGANT, OI BILLIE, FRANCE.

EBOGESS' FOE EXTBACTING GLYCERIN 3301i. 'VEEIQAISSES'.

1,078,580., Specification of Letters Iatent.

Patented Nov. 11,1913. No Drawing.

Application filed. September 7, 1.91.2. Serial No. 719,1).

decantation on the one hand glycerin and on the other hand amyl alcohol which is thus recovered for reuse inthe process.

The following description will explain the method of operation which forms the application oi the principle of the invention to the treatment of vinasses from molasses and from grain To all whom it may concern:

Be it known that we, Gasron PHILIPPE GUIGNARD and IIENRI Louis AooLrHn Manna WA'rnnr-mrr, both citizens of the Republic. of France. and residing, respectively, at Avenue des Marronniers, 'elun, Seine-et- Marne, and at 80 Quai de la Basse Deule, Lille, Nord, France, have invented a new and useful Process for Extracting Glycerin from Vinasses, of which the tollowing is a specification.

The processes for extracting the glycerin contained in distillery v'inasses, based upon ihe nethodical washing of the more or less dried vinasses, all present disadvantages. ll'or if the vinasses are not absolutely dry, the glycerin-solvent becomes hydrated and dissolves substances which would be insoluble in the anhydrous solvent. On the other hand, the glycerin which dissolves in the solvent is itself a solvent of numerous metal-- lic salts. The glycerin obtained under these conditions is not pure and it must be subjected to a process of rectification; this rectificati-on, conducted in presence of metallic salts, involves the destruction of a portion of the glycerin recovered. The only processi 1n based upon thew ideas and at present capav (0 The liquid separated from the see bio of yielding glycerin. free from impart precipitateisevaporated to dryness, first in ties rests upon the complete desiccation of theknown regenerative the vinasses and themse or absolute alcohol. i apparatus, and lastly "n the apparatus which This process form-s the subject of our coforms the subject of the Letters Patent No. pending application Serial 0. 630,206, filed 1,036,486, granted August 20, 1912,

conditions (cl) The dry residue which contains the May 29th. 1911. However, the of this process, though possible in practice, remainder of the solid substances constltu 3 ing the vinasses to the followare comparat vely illicult to carry out. is submitted The present invention relates to a process ing systematic w-ashings:--{d) Washing for extracting the glycerin, which forms actually an analytical method and rests upon the following-bases: (1) Desiccation of the vinassesas far as possible without it being,"

I. T 'reatment of oinasses from molasses.

(a) To the molasses-vinasses there is added a small quantity of tannin or of a solution of tannic extract which precipitates the nitrogenous substances of pepto-lic nature. The recipitate is collected and dried. This rst separation renders the further desiccation easier.

(b) Tothe liquid resulting from this separation there v is added ferric hydrate 1%,(01-1), or ferric chlorid Fe Cl and the liquid is then rendered alkaline by means of lime Ca(OH) a The excess of lime is new traliaed either by carbonic acid gas obtained from the vats or by a small quantity of so diuiu carbonate e430,. There is obtained ,a precipitate which contains certain organic acids, particular succinic acid ,H.,O,'.

malate of otassium'; the acetone is separated by distillation to return into the operation. The potassium malate isalso sepan albuminoid or while cold with acetone which dissolves the 7 necessary that thisdesiccation be complete arated and there are extracted therefrom (2) l/Vashing of the residue with venous malic acid and potassium salts, or else by calcination in .a closed retort potassium carbonate and various volatile products. The washin with acetone leaves a residue which is en jected while hot or cold, to a methodical washing with This solvent removes various urifermente lucoses such as raflinose' at amino; these products may be separate by fractional crystallization, if necessary. (0?) The solid residue of the washing wit ethyl acetate is washed while heated with hot amyl alcohol which dissolves only the liquids in which. glycerin is insoluble under the conditions of the operation, inorder to separate the substances which would dissolve in alcohol at the same time as the (3) -Washing of the residues of the wi h hot amyl alcohol previous washings, with heat, in order to dissolve the glycerin. Glycerin is very soluble in hot amyl alcohol but is insoluble or very slightly soluble in cold amyl alcohol; it is, therefore, only to separate the two liquids and to obtain by the same time as ethyl acetate.

glycerin. The amyl solution of gylcerin when cooled separates into two liquids (1) gylcerin, (2) amyl alcohol saturated when cold with glycerin, and which may be recovered for reuse in the process.

The washing with hot amyl alcohol could not be effected upon the whole of the vinasses, because the potassium malate and the betai'ne would also be dissolved at the same time as the glycerin. On the other hand, a first modification of the process according to the present invention, consists in washing the whole of the vinasses with cold amyl alcohol saturated with glycerin. This washing removes the potassium malate and the betai'ne without dissolving any more glycerin, and replaces the operations d and d previously described; by following this cold washing by a hot washing with hot amyl alcohol, the glycerin alone is removed and can be separated from the alcohol bycooling.

A. second modification of the process consists in washing the dry residue resulting from the operation with ethyl acetate, which removes at the same time the potassium malate, the unfermented glucose and the betai'ne. Distillation of the solution yields the solventand a mixture of solid substances which are separated by crystallization.

[1. Treatment of grainwtnaaaes.

Two cases may be considered:

1. The whole of the .vinasses are treated.

2. The vinasses are divided-by decantation into a solid portion and a liquid portion.

1. Treatment of the whole of the otnasses.The vinasses are neutralized with carbonate of lime and conveyed to the evaporating apparatus. The dry'residue is subjected successively to :'(a) a methodical Washing with acetone which removes the fatty matter; in place of acetone. there may be employed carbon tetrachlorid, benzin, etc. It is absolutely necessary to remove the fatty matter before dissolving the glycerin with amyl alcohol, because the fatty substances are also soluble in amyl alcohol, and because the absolute solubility of fatty The liquid portion,

oreeeo matter and of glycerin in amyl alcohol diminishes when fatty matter and glycerin are present. (6) A methodical washing in hot amyl alcohol which dissolves the glycerin, the latter being separated by cooling.

2. Treatment of decanted oinassea-The solid portion is used as suits the distiller. at present lost and wasted in the residual liquor, may with advantage be treated as follows :'lhe vinasses are neutralized with ferric hydrate and carbonate of lime. There is obtained a precipitate of succinate of iron from which succinic acid may be extracted. The liquid, which may or may not be separated from the precipitate, is evaporated to dryness and subjected to hot washing with hot amyl alcohol in order to recover It is to be noted that the fatty matter remains in the solid portion, which renders it useless to effect a preliminary washing with a solvent of fatty matter. The glycerin is separated from the amyl alcohol by cooling.

The solid residue of the washing with amyl alcohol is composed of lactate of lime, nitrogenous matter, phosphates, and potassium salts, and forms an excellent manure.

What we claim and desire to secure by Letters Patent of the United States is process for extracting glycerin from vinaszrcs which comprises dcsiccating the vinasses, washing the residue with liquid in which glycerin is insoluble under the conditions ofthe operation, but capable of dis solving substances which would dissolve in .amyl alcohol together with the glycerin,

then Washing the residue of these washings in hot amyl alcohol to dissolve the glycerin alone, and then cooling the amyl alcohol to separate the glycerin therefrom.

In testimony whereof We have signed our names to this specification, in the presence of two subscribing Witnesses.

GASTON PHILIPPE GUIGNARD.

HENRI LOUIS ADOLPHE MARIE WATRIGANT.

Witnesses.

H. C. OoxE.

LiioN PEILLnT.

the glycerin. 

